Heterocyclic quaternary ammonium derivatives of alpha-halogen carboxy acid esters of oxyalkylated phenol-aldehyde resins



Patented Jan. 8, 1952 HETEROCYCLIC QUATERNAR-Y AMMONIUM DERIVATIVES FALPHA-HALOGEN CAR- BOXY ACID ESTERS OF OXYALKYLATED PHENOL-ALDEHYDERESINS Melvin De Groote, University City, and Bernhard Keiser, WebsterGroves, M0., assignors to Petrolite Corporation, Ltd., Wilmington, Del.,a. corporation of Delaware No Drawing. Application December 13, 1948,

1 Serial No. 65,083

13 Claims. (01. 260-53) The present invention is concerned with certainnew chemical products, compounds or compositions which have usefulapplication in various arts. This invention is a continuation-inpart ofour copending application Serial No. 726,206, filed February 3, 1947,and now abandoned. It includes methods or Procedures for manufacturingsaid new chemical products, compounds, or compositions, as well as theproducts, compounds or compositions themselves. Said new compounds orcompositions are quaternary ammonium compounds obtained by reactionbetween a heterocyclic compound of the pyridine series, consisting ofpyridine, quinoline, isoquinoline and carbon-linked methyl homologuesthereof, and the ester of an alpha-halogen monocar boxylic acid havingnot over 6 carbon atoms. Specifically, the esters just referred to,being the reactants for combination with the tertiary amino-compound,are hydrophile synthetic products being oxyalkylation products of (A) analpha-beta alkylene oxide having not more than 4 carbon atoms andselected from the class consisting of ethylene oxide, propylene oxide,butylene oxide, glycide, and methylglycide; and (B) anoxyalkylation-susceptible, fusible, organicsolvent soluble,water-insoluble, phenol-aldehyde resin; said resin being derived byreaction between a difunctional monohydric phenol and an aldehydehavingnot over 8 carbon atoms and reactive towards said phenol; said resinbeing formed in the substantial absence of trifunctional phenols; saidphenol being of the formula:

in which R is a hydrocarbon radical having at least 4 and not more than12 carbon atoms and substituted in th 2, 4, 6 position; saidoxyalkylated resin being characterized by the introduction into theresin molecule of a plurality of divalent radicals having the formula(R1O)n, in whichRiis a member selected from the class consisting ofethylene radicals, propylene radicals, butylene radicals,hydroxy-propylene radicals, and hydroxybutylene radicals, and n is anumeral varying from 1 to 20 with the proviso that atv least 2 moles ofalkylene oxide be introduced for each phenolic nucleus.

'Although the herein described products have a'number of industrialapplications, they are of particular value for resolving petroleumemulsions Of the water-in-oil type, that are commonly referred to as cutoil, roily oil, emulsified oil, etc., and which comprise fine dropletsof naturally-occurring waters or brines dispersed in a more or lesspermanent state throughout the oil which constitutes the continuousphase of the emulsion. This specific application is described andclaimed in our co-pending application Serial No. 65,082, filed December13, 1948, now Patent 2,542,001, granted February 20, 1951. The newproducts are useful as wetting, detergent and leveling agents in thelaundry, textile and dyeing industries; as wetting agents and detergentsin the acid washing of building stone and brick; as wetting agents andspreaders in the application of asphalt in road building and the like;as a flotation reagent in the flotation separation of various aqueoussuspensions containing negatively charged particles, such as sewage,coal washing waste water, and various trade wastes and the like; asgermicides, insecticides, emulsifying agents, as, for example, forcosmetics, spray oils, water-repellent textile finishes; as lubricants,etc.

The oxyalkylated resins, used to provide the alcoholic radical of thealpha-halogen monocarboxylic acid esters converted to the new quaternaryammonium compounds of the invention are described in our Patent2,499,370, granted March 7, 1950, and the alpha-halogen monocarboxylicacid esters which are converted to the quaternary ammonium compounds ofthe invention, as well as the oxyalkylated resins, are described in ourPatent 2,542,001, granted February 20, 1951, and reference is made tothese patents for description of the phenol-aldehyde resins used andtheir oxyalkylation and conversion to alpha-halogen monocarboxylic acidesters. For specific examples of the resins, reference is made toExamples 1a through 103a of Patent 2,499,370. For examples of theiroxyalkylation, reference is made to tables which appear at columns 31through 46 of Patent 2,542,001. For examples of the esters of theseoxyalkylated resins with alpha-halogen monocarboxy acids, reference ismade'to Examples 10 through 390 of Patent 2,542,001.

The thermoplastic resins employed as raw materials are hard, brittle,resins, varying in color from a pale pink to a dark amber. Theoxyalkylated resins derived from the thermoplastic resins vary fromresinous or sub-resinous materials to thick oils or wax-like bodies. Thecolor, as a result of the next reaction, is apt to be much darker inappearance, varying from honey color to a deep brown or amber. Such oilor subreaction, may be illustrated as follows:

Eta

H 64H: O(C2H40),,0O.CCl n HCH l C H H '01 i o owzulonpog.

Having obtained the halogenated acid ester, such as the chlorcaceticacid ester of the kind previously described and the hydroxylated highmola-l amine, as specified, all that is required is to react theproducts so as to form a quaternary ammonium compound, all of which maybe illustrated by the following examples:

Example 111 The chlorine-containing reactant employed was an esteridentified as Example c of Patent 2,542,001. 400 grams of thisxylene-containing ester were mixed with an equimolar amount of pyridine,i. e., 12.8 grams, and the product refiuxed at the boiling point ofxylene (140 to 150 C.) for 2 to 4 hours. Prior to refluxing, an amountof xylene approximately equal to one-fourth the tertiary amine, wasadded. In thisinstance it was 5 grams.

. Although in the instant experiment, and those subsequently noted, thesolvent employed was xylene, one may employ cymene or decalin. Thereaction takes place at comparatively low temperature, as previouslysuggested, and, in any event, under 215 C., and frequently as low as 120C. A convenient temperature of reactionis 140 to 160 C. Thus, if xyleneis employed, as is our preference, and if there is present at least 25%,by weight, of the combined reactants in the form of xylene, there is theautomatic effect in regard to the temperature, and the xylene may bepermitted to remain after the reaction is complete. If desired, it maybe eliminated in any convenient manner, suchas distillation or vacuumdistillation. In all cases we have used a time period of 2 to 4 hoursand found thereaction was complete at the end of the 4-hour period. Insome cases we believe the reaction was complete in 30 to 45 minutes. Inthis particular reaction, and in most of the subsequent reactions, wehave attempted to have sufficient xylene present, adding more, if needbe, so the final reaction product contains approximately 45% xylene and55% quaternary compound. A solution of this concentration is usuallyfree from any highly viscous or tacky properties, and is convenient foruse. in a pump, which is particularly desirable when used as ademulsifier. The final product obtained was amber in color,water-soluble, and contained 46.5% xylene.

Example 2d 4 acted with 10 grams of alpha-picolme. The final product wasa deep amber-colored liquid, fairly water-soluble, and contained 47%xylene.

Example 30! The same procedure was followed as in Example 1d, preceding,except that 400 grams of the ester identified as 130 of Patent 2,542,001were reacted with 19.5 grams of pyridine. The final product was anamber-colored, water-soluble liquid, containing 52.5% xylene.

Example 4d The same procedure was followed as in Example ld, preceding,except that 400 grams of the ester identified as 140 of Patent 2,542,001were reacted with 15.9 grams of pyridine. The final product was anamber-colored, water-soluble liquid, containing 50% xylene.

Example 5d "The same procedure was followed as inExample 1d, preceding,except that 400 grams of the ester identified as of Patent 2,542,001were reacted with 19.6 grams of pyridine. The final product was anamber-colored, water-,emulsifiable liquid, containing 49.5% xylene.

Example 611 The same procedure was followed as in Example 1d, preceding,except that 400 grams of the ester identified as of Patent 2,542,001were reacted with 15.9 grams of pyridine. The final product was anamber-colored, watereemulsiflable liquid, containing 48.4% xylene.

Example 7d The same procedure was followed as in Example ld, preceding,except that 400 grams offthe ester identified as 20 of Patent 2,542,001were reacted with 26 grams of pyridine. The final product was anamber-colored, water-soluble liquid, containing 55% xylene.

Example 8d The same procedure was followed as vin-Example 1d, preceding,except that 400 grams of the ester identified as of Patent 2,542,001were reacted with 22 grams of pyridine. The final product was anamber-colored, Watersoluble liquid, containing 59.5% xylene.

Example 9d The same procedure was followed as in Example ld, preceding,except that 400 grams of the ester identified as 19c of Patent 2,542,001were reacted with 16 grams of pyridine. The final product was a deepamber-colored, very water-soluble liquid, containing 47.5% xylene.

Example 10d The same procedure was followed as in Example ld, preceding,except that 400 grams of the ester identified as of Patent 2,542,001were reacted with 19.7 grams ofpyridine. The'fin'al product was a deepamber-colored, somewhat viscous, water-soluble liquid, containing 48.7%xylene.

Example 1101 The same procedure was followed as in' Example ld,preceding, except that 400 gramso'f the ester identified as 200 ofPatent 2,542,001 were reacted with 13.6 grams of pyridine. The

final product wasa deep amber-colored, water- 5 emulsifiable liquid,containing 46% xylene.

Example 12d The same procedure was followed as in Example ld, preceding,except that 400 grams of the ester identified as 30 of Patent 2,542,001were reacted with 16.8 grams of pyridine. The final product; was anamber colored, water soluble liquid, containing 47% xylen Example 13dThe same procedure was followed as in Example ld, preceding, except that400 grams of the ester identified as 4c of Patent 2,542,001 were reactedwith 18.2 grams of pyridine. The final product was a deep amber-colored,slightly cloudy, water-soluble liquid, containing 45% xylene.

Example 14d The same procedure was followed as in Ex-- ample 1d,preceding, except that 400 grams of the ester identified as 230 ofPatent 2,542,001 were reacted with 22.8 grams of pyridine. The finalproduct was a deep amber-colored, water-soluble liquid, containing 43%xylene.

Emample 16d The same procedure was followed as in Example ld, preceding,except that 400 grams of I the ester identified as 240 of Patent2,542,001 were reacted with 22.5 grams of alpha-picoline. The finalproduct was a deep amber-colored, water-soluble-liquid containing 43%xylene.

Example 17d The same procedure was followed as in Example 1d, preceding,except that 400 grams of the ester identified as 250 of Patent 2,542,001were reacted with 17.3 grams of alpha-picoline. The final product was adeep amber-colored, wator-soluble, slightly cloudy liquid, containing42.5% xylene.

Having thus described ourinvention, what we claim as new and desire tosecure by Letters Patent is:

L A 1 quaternary ammonium compound obtained by reaction between aheterocylic compound of the pyridine series consisting of pyr-' idine,quinoline, isoquinoline, and carbon-linked methyl homologues thereof,and an ester in which the acyl radical is that of an alpha-halogenmonocarboxylic acid having not over 6 carbon atoms and composed ofcarbon, hydrogen, oxygen and halogen and the alcoholic radical is thatof certain hydrophile polyhydric synthetic products; said hydrophilesynthetic products being oxyalkylation products of (A) an alpha-betaallrylene oxide having not more than 4 carbon atoms and selected fromthe class-consisting of ethylene oxide, propylene oxide, butylene oxide,glycide, and methylglycide; and (B) an oxyalkylation-susceptible,fusible, organic solventsoluble, water-insoluble, phenolaldehyde resin;said resin being derived by reaction between a difunctional monohydricphenol and an aldehyde having not over 8 carbon atoms and having onefunctional group reactive towards said phenol;

said resin being formed in the substantial absence in whichR is ahydrocarbon radical having at least 4 and not more than'12 carbon atomsand substituted inone of the positions ortho and para; said oxyalklatedresin being characterized by the introduction into the resin molecule atthe phenolic hydroxyls of a plurality of divalent radicals having theformula (R10)n, in which R1 is a member selected from the classconsisting of ethylene radicals, propylene radicals, butylene radicals,hydroxypropylene .radicals, and hydroxybutylene radicals, and n is anumeral varyingifroml to 20; with the proviso that at least 2 moles ofalkylene oxide be. introduced for each phenolic nucleus.

v2. A quaternary ammonium compound obtained by reaction between aheterocyclic compound of the pyridine series consisting ofpyridine,quinoline, isoquinoline, and carbon-linked. methyl homologues thereof,and a chloroacetate of certain hydrophile polyhydric synthetic products;said hydrophile synthetic products being oxyalkylation products of (A)an alpha-beta alkylene oxide having not more than 4 carbon atoms andselected from the class consisting of ethylene oxide, propylene oxide,butylene oxide,-

glycide, and methylglycide; and (B) an oxyalkylation-susceptible,fusible, organic solvent-.

soluble, water-insoluble phenolaldehyde resin;

said resin being derived by reaction between a difunctional monohydricphenol and an aldehyde having not over 8 carbon atoms and having onefunctional group reactive towards said phenol; said resin being formedin the substantial absence of phenols of functionality greater than two;said phenol being of the formula:

in which R is a hydrocarbon radical having "at least 4 and not more than12 carbon atoms and substituted in one of the positions ortho and para;said oxyalkylated-resin being characterized by the introduction into theresin molecule at the phenolic hydroxyls ofa plurality of divalentradicals having the formula (B10911, in which R1 is a member selectedfrom the class consisting. of ethylene radicals, propyleneradicals..butylene radicals, hydroxypropylene radicals, and hydrox-.

ybutylene radicals, and n is a numeral varying from 1 to 20;. withthe-proviso that at least 2 moles of alkylene oxide be introduced foreach phenolic nucleus; and with the final proviso that the hydrophileproperties of the ultimate quaternary ammonium compound as well as theoxyalkylated resin in an equal weight of xylene are sufficient toproduce an emulsion when said xylene solution is shaken vigorously withoneassrssc ucts; aid hydrophil'e. synthetic products being oxyethylatlonproducts of (A) ethylene oxide;

in which R is a hydrocarbon radical having at least 4 and not more than12 carbon atoms and substituted in one of the positions ortho and para;said oxyethylated resin being characterized by the introduction into theresin molecule at the phenolic hydroxyls of a plurality of divalentradicals having the formula (Cal-I40) 11., wherein n is a'numeralvarying from 1 to 20; with the proviso that at least 2 moles of ethyleneoxide be introduced for each phenolic nucleus; and with the finalproviso that thehydrophile properties of the ultimate quaternaryammonium compound as well as the oxyethylated resin in an equal weightof xylene are sumcient to produce an emulsion when said xylene solutionis shaken vigorously with one to three volumes of water.

4. A quaternary ammonium compound obtained by reaction between pyridineand chloroacetate of certain hydrophile polyhydric synthetic products;said hyd'rophile synthetic products being oxycthylaticn products of (A)ethylene oxide, and (B) an oXyethylation-susceptible, fusible, organicsolvent-soluble, water-insoluble, low-stage, phenol-aldehyde resinhaving an average molecular. weight corresponding to at least 3 and notover 7 phenolic nuclei per resin molecule; said resin being derived byreaction between a difunctional monohydric phenol and formaldehyde; saidresin being formed in the substantial absence of phenols offunctionality greater than two; said phenol being of the formula:

which. R is an aliphatic hydrocarbon radical having at least 4 and notover 12 carbon atoms and substituted in one of the positions ortho andpara; said oxyethylated resin. being characterized by the introductioninto the resin molecule at the phenolic hydroxyls of a plurality ofdivalent radicals having the formula (C2H4O) n; wherein n is. a numeralvarying from 1 to 20; with the proviso that at least 2 moles of ethyleneoxide be introduced for each phenolic nucleus; and with the finalproviso that the hydrophile properties of theultimate quaternaryammonium. compound as well. as the oxyethylated resin in an equal weightof xylene are suificient to produce an emulsion when said xylenesolution isrshaken vigorously with one to three volumes of water.

5. A quaternary ammonium compound ob: tained byreaction between pyridineand a chloroacetate of certain hydrophile polyhydric synthetic products;said hydrophilesynthetic products being oxyethylation products of (A)ethylene oxide, and (B) an oxyethylation-susceptible, fusible, organicsolvent-soluble, water-insoluble, low-stage, acid-catalyzed.phenol-aldehyde resin having an average molecular weight correspondingto at least 3 and not over 7 phenolic nuclei per resin molecule; saidresin being derived by reaction between a difunctional monohydric phenoland formaldehyde; said resin being formed in the substantial absence ofphenols of functionality greater than two; said phenol being of theformula:

in which R is an aliphatic hydro-carbon radical having at least l andnot over 12 carbon atoms and substituted in one of the positions orthoand para; said oxyethylated resin being characterized by theintroduction into the resin molecule at the phenolic hydroxyls of aplurality of divalent radicals having the formula (.CzHrOln; wherein nis a numeral varying from 1 to 20; with the proviso that at least 2moles. of ethylene oxide be introduced for each phenolic nucleus; andwith the final proviso that thehydrophile properties of the ultimatequaternary ammonium compound as well as the o-xyethylated resin in anequal weight of xylene are sufficient to produce an emulsion when saidxylene solution is shaken vigorously with one to three volumes of water.

6. The product of claim 4, wherein R is substituted in the paraposition.

'7. The product of claim 4, wherein R is a butyl:

radical substituted in the para position.

8. The product of claim 4; wherein R is an arnyl radical substituted inthe para position.

9- The product of claim 4, wherein R is. a

mind radical substituted in the para position.

10. The product of claim 5, wherein R is substituted in the paraposition.

II. The product of claim 5, wherein R- is a butyl radical substituted inthe para position.

12. The product of claim 5, wherein R is an amyl radical substituted inthe para position.

13. The product of claim 5, wherein R is a nonyl radical substituted in.the para position. MELVIN DE GROOTE.

BERNHARD KEISER.

REFERENCES CITED UNITED STATES PATENTS Number Name Date D Groote Mar. 7,l9 50

1. A QUATERNARY AMMONIUM COMPOUND OBTAINED BY REACTION BETWEEN AHETEROCYCLIC COMPOUND OF THE PYRIDINE SERIES CONSISTING OF PYRIDINE,QUINOLINE, ISOQUINOLINE, AND CARBON-LINKED METHYL HOMOLOGUES THEREOF,AND AN ESTER IN WHICH THE ACYL RADICAL IS TAHT OF AN ALPHA-HALOGENMONOCARBOXYLIC ACID HAVING NOT OVER 6 CARBON ATOMS AND COMPOSED OFCARON, HYDROGEN, OXYGEN AND HALOGEN AND THE ALCOHOLIC RADICAL IS THAT OFCERTAIN HYDROPHILE POLYHYDRIC SYNTHETIC PRODUCTS; SAID HYROPHILESYNTHETIC PRODUCTS BEING OXYALKYLATION PRODUCTS OF (A) AN ALPHA-BETAALKYLENE OXIDE HAVING NOT MORE THAN 4 CARBON ATOMS AND SELECTED FROM THECLASS CONSISTING OF ETHYLENE OXIDE, PROPYLENE OXIDE, BUTYLENE OXIDE,GLYCIDE, AND METHYLGLYCIDE; AND (B) AN OXYALKYLATION-SUSCEPTIBLE,FUSIBLE, ORGANIC SOLVENTSOLUBLE, WATER-INSOLUBLE, PHENOLALDEHYDE RESIN;SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRICPHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND HAVING ONEFUNCTIONAL GROUP REACTIVE TOWARDS SAID PHENOL; SAID RESIN BEING FORMEDIN THE SUBSTANTIAL ABSENCE OF PHENOLS OF FUNCTIONALITY GREATER THAN TWO;SAID PHENOL BEING OF THE FORMULA: